CN105838009A - Absorbent polymer and method of preparing the same - Google Patents
Absorbent polymer and method of preparing the same Download PDFInfo
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- CN105838009A CN105838009A CN201610048746.9A CN201610048746A CN105838009A CN 105838009 A CN105838009 A CN 105838009A CN 201610048746 A CN201610048746 A CN 201610048746A CN 105838009 A CN105838009 A CN 105838009A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F2/00—Processes of polymerisation
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- C08F2/10—Aqueous solvent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
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- Absorbent Articles And Supports Therefor (AREA)
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Abstract
An absorbent polymer has an absorbency under pressure (AUL) ranging from 20 to 45 g/g; a phase angle (delta) of swollen gel ranging from 3 to 30 degrees; and a decrease in phase angle ranging from 3 to 35%. Thereby, the absorbent polymer may have favorable gel elasticity under pressure after swelling, so as to reduce adhesion between swollen particles. Accordingly, even after absorbing the liquid to swell the absorbent polymer, the polymer may maintain excellent flow conductivity, thereby reducing a decrease in absorption ability of the absorbent polymer.
Description
Technical field
The present invention relates to water-absorbing resins of a kind of good water absorption and preparation method thereof.
Background technology
Super absorbent resin (Super Absorbent Polymer, SAP) refers to absorb the decades of times of own wt
Synthetic high polymer matter to the moisture of hundreds times.Owing to super absorbent resin has after absorbing moisture, even if applying arbitrary
The pressure of size, also will not discharge the strong moisture holding capacity of absorbed moisture, and therefore, the health in diaper and sanitary towel etc. is used
The material of product is widely used.
This super absorbent resin is along with the high performance of the hygienic article such as the diaper as its main uses, it is desirable to its
Multiple physical property excellent.Specifically, can enumerate such as free water absorbing force, absorption speed, water dissolvable composition, add pressure suction
Water multiplying power, water holding capacity and logical fluidity etc..In order to improve described physical property, the most persistently propose multiple for improving resin table
The method of the crosslink density of surface layer.
In described various physical property items, when with water-absorbing resins because of urine or body fluid and by swelling after characteristic phase
The water dissolvable composition closed, logical fluidity, add the physical property of pressure water absorbent rate and water holding capacity etc. low time, this can become to thing
The life of product user brings offending reason.The article being added with water-absorbing resins are the most repeatedly exposed to urine
Or in body fluid, at this point it is important to the permeability for liquids of swelling gel under pressure.Infiltration when the water-absorbing resins through swelling
Property low time, the unhappiness of user can be caused, such as, be only exposed to the part of urine or body fluid by local swelling so that
The volume of specific part increases, or urine or body fluid are difficult to be absorbed well by the resin within article, and is being positioned at article
The resin surface layer flowing etc. on surface.But, when permeability is good, urine or body fluid as liquid are to the suction being included in article
Water-base resin entirety is scattered equably and is absorbed, so that user feels more comfortable.
The permeability of water-absorbing resins as above, under logical wirking pressure, gel blocking (Gel-blocking) phenomenon is come
Illustrating, under pressure, gel blocking phenomenon is the most serious, and body fluid more can not pass through swelling gel, and only by local absorption, finally exists
It is positioned at the Surface runoff of the gel on surface.This can become the very important factor of the physical property reducing water-absorbing resins.
Disclosing a kind of high water-absorbent resin composition in US granted patent the 8466228th, described compositions comprises
Single vinyl unsaturated monomer is by partially polymerized resin, thus under swelling state, liquid handling capability is excellent, and has
High moisture holding capacity.But, solutions to solve the above problems were is not proposed.
[prior art literature]
[patent documentation]
US granted patent the 8466228th
Summary of the invention
Solve the technical problem that
It is an object of the invention to, it is provided that after a kind of swelling, also show that the water-absorbing resins of the physical property of excellence, institute
State water-absorbing resins and there is the water absorption of excellence, and the elasticity of water-absorbent besin particles through swelling can be improved, thus
Improve Test Liquid Permeability of Core.
Technical scheme
1. a preparation method for water-absorbing resins, the preparation method of described water-absorbing resins comprises the following steps: make bag
Polymeric compositions polymerization containing acrylic monomer, polysaccharide and cross-linking agent；And be dried and pulverize obtain through above-mentioned polymerization
The aqueous gel arrived, and, in terms of the acrylic monomer of polymeric compositions, comprise the described polysaccharide of 0.1 to 20 weight %.
2., in the preparation method of the water-absorbing resins of described 1, described polysaccharide is selected from alginate, K-carrageenan
(kappa-carrageenan), I-carrageenan (iota-carrageenan), lambda-carrageenan (lambda carrageenan),
At least one in pectin, Rhizoma amorphophalli and cellulose.
3., in the preparation method of the water-absorbing resins of described 1, in terms of the acrylic monomer of polymeric compositions, comprise
The described polysaccharide of 0.5 to 10 weight %.
4. a preparation method for water-absorbing resins, the preparation method of described water-absorbing resins comprises the following steps: make bag
Polymeric compositions polymerization containing acrylic monomer and cross-linking agent；Mix and mediate the aqueous gel obtained through above-mentioned polymerization
And polysaccharide；And it is dried and pulverizes the described aqueous gel through mediating, and, with the acrylic monomer of polymeric compositions
Meter, comprises the described polysaccharide of 0.1 to 20 weight %.
5., in the preparation method of the water-absorbing resins of described 4, described polysaccharide is selected from alginate, K-carrageenan, I-
At least one in carrageenan, lambda-carrageenan, pectin, Rhizoma amorphophalli and cellulose.
6., in the preparation method of the water-absorbing resins of described 5, in terms of the acrylic monomer of polymeric compositions, comprise
The described polysaccharide of 0.5 to 10 weight %.
7. a water-absorbing resins, pressure water absorbent rate (AUL) that adds of described water-absorbing resins is 20 to 45g/g；Swelling
The phase angle (δ) of gel is 3 to 30 degree；Phase angle slip (%) is 3 to 35%.
8., in the water-absorbing resins of described 7, pressure water absorbent rate (AUL) that adds of described water-absorbing resins is 30 to 45g/
g。
9., in the water-absorbing resins of described 7, the phase angle (δ) of the swelling gel of described water-absorbing resins is 3 to 20 degree.
10., in the water-absorbing resins of described 7, the phase angle (δ) of the swelling gel of described water-absorbing resins is 3 to 10
Degree.
11. in the water-absorbing resins of described 7, and the phase angle slip (%) of described water-absorbing resins is 5 to 35%.
12. in the water-absorbing resins of described 7, and the phase angle slip (%) of described water-absorbing resins is 10 to 35%.
13. in the water-absorbing resins of described 7, and the particle size distribution of described water-absorbing resins is 100 to 1000 μm.
Beneficial effect
The water-absorbing resins of the present invention due under the pressure after swelling gel elastomer good, therefore, it is possible to reduce through swelling
Intergranular attachment.Thus, it also is able to maintain the permeability of excellence after swelling at absorption liquid such that it is able to reduce water absorption
The reduction of the water absorbing capacity of resin.
Accompanying drawing explanation
Fig. 1 is the accompanying drawing summarized and illustrate the structure measuring the device adding pressure water absorbent rate.
Detailed description of the invention
The present invention relates to one adding pressure water absorbent rate (AUL) is 20 to 45g/g；The phase angle (δ) of swelling gel be 3 to
30 degree；Phase angle slip (%) is water-absorbing resins of 3 to 35% and preparation method thereof.Described water-absorbing resins is owing to having
Features described above, the gel elastomer therefore having had under the pressure after swelling such that it is able to reduce intergranular through swelling
Attachment, thus, also is able to maintain excellent permeability such that it is able to reduce the suction of water-absorbing resins at absorption liquid after swelling
The reduction of outlet capacity.
Pressure water absorbent rate (AUL) expression that adds in the present invention uses the artificial urine prepared by following method to replace physiology
Saline, and the value measured according to following test example 1.Described artificial urine is to weigh the sodium chloride of 6g, the potassium chloride of 4g, 0.6g
After the magnesium chloride of calcium chloride and 0.3g, add ultra-pure water and be adjusted to 1000g, and stir 1 hour and prepare.
The phase angle (δ) of the swelling gel in the present invention refers to, rotates described artificial urine same of 20g with 500rpm
Time, after putting into the water-absorbing resins of 1g, and the prepared gel making water-absorbing resins swelling 20 times (weight basis), utilize first influent stream
Become the parallel-plate (parallel plate) of extension system (ARES) flow graph, with 35 DEG C, 5% tension, measure viscosity system
Number and the ratio of coefficient of elasticity, and the angularly value that converts.
In the present invention, phase angle slip (%) is, measures water-absorbing resins respectively by ultra-pure water and described artificial urine
Come the phase angle of the swelling gel after swelling 20 times (weight basis), and substitute into following mathematical expression 1 and the value that obtains, i.e. represent
Relative resilient increment rate relative to the gel by artificial urine swelling of ultra-pure water.
[mathematical expression 1]
Phase angle slip (%)=[phase angle (ultra-pure water)-phase angle (artificial urine)]/phase angle (ultra-pure water) × 100
According to a specific example of the present invention, it is provided that it is 20 to 45g/g that one adds pressure water absorbent rate (AUL), swelling gel
Phase angle (δ) be 3 to 30 degree, phase angle slip (%) is the water-absorbing resins of 3 to 35%.
Water-absorbing resins according to the present invention meet replace saline solution and use above-mentioned artificial urine add pressure water absorbent rate
It it is the physical property of 20 to 45g/g.
If the pressure water absorbent rate that adds of water-absorbing resins meets the numerical value of above-mentioned scope, then in the product of diaper etc.
When using as absorber, can have the sufficient moisture absorption amount making the imperceptible offending degree of user, and
Extraordinary aspect is, the pressure applied in life activity is had sufficient water branch support force.
If the pressure water absorbent rate that adds of the water-absorbing resins according to the present invention is less than 20g/g, then wears in life and make
During with the water suction articles for use of described water-absorbing resins, owing to the water absorption under the pressure that applies is low, user can be made to feel displeased
Fast or need often to change water suction articles for use, if greater than 45g/g, then can excessively absorb moisture, thus the intensity meeting of swelling gel
Die down, cause gel frangible, thus the moisture absorbed can dissolution again.For the absorber as product, water-absorbing resins
Add pressure water absorbent rate and be preferably 30 to 45g/g.
It addition, swelling gel phase parallactic angle (δ) and phase angle slip (%) according to the water-absorbing resins of the present invention have
Specific scope.
Gap blocking between swelling gel can illustrate with adherence mechanism between the granule of following 5 kinds.1) mechanicalness adheres to；
2) chemical adheres to；3) adhesion caused by dispersion force；4) electrically adhere to；5) adhesion caused by extension.
Surface generally, due to water-absorbing resins is electronegative, and therefore, in terms of electricity, repulsive force works, thus electricity consumption
Property adherence mechanism can not illustrate the adhesion of water-absorbing resins, and owing to resin will not occur chemical reaction under swelling state,
Therefore can not illustrate with chemical adherence mechanism.Therefore, in order to the adhesion of the water-absorbing resins through swelling is described, need
Consideration is through mechanicalness physical property, dispersion force and the extension etc. of the resin of swelling.
Wherein, mechanicalness adherence mechanism becomes the main cause of adhesion between the granule of water-absorbing resins.Through swelling
Water-absorbing resins make moisture become most constituent because absorbing the body fluid of decades of times of own wt, therefore machine
Tool physical property is the most weak.Thus structure is easily deformed when applying pressure, and final making under stress does not has between granule
The attachment of ground, gap.This attachment caused by mechanical distortions can become under pressure the important former of gap blocking between swelling granule
Cause.
Water-absorbing resins, after swelling, under stress can cause gap to block because of the attachment between absorbent particle,
Thus reduce its permeability.After swelling gel is under pressure, its form can change, in the situation that elasticity is weak and viscous characteristics is strong
Under, its metamorphosis is serious, and granule and intergranular gap can be reduced.If it occur that intergranular blocking, then liquid is not
Can flow to internal, and flow by local absorption or in the swelling gel surface of blocking, so that user feels unpleasant.When
During distress resolves, if swelling gel does not have elasticity, then will not restore, therefore, granule can keep the state mutually bonded, and
And water suction physical property to liquid after being greatly reduced.
As previously described, present inventors have realized that the mechanicalness physical property of swelling gel is relevant with permeability,
It is especially recognized that the permeability of phase angle and the swelling gel obtained from the viscosity of swelling gel and the ratio of coefficient of elasticity
There is close association, thus propose the present invention.Specifically, the value at the phase angle determined is the least, represents swelling gel
Elasticity is the biggest, and gets over relative to the slip at the phase angle of the gel with ultra-pure water swelling with the phase angle of artificial urine swelling
Greatly, represent that gel elasticity in artificial urine is the most excellent.
It is 3 to 30 degree (°) that water-absorbing resins according to the present invention meets the phase angle of the swelling gel in artificial urine
Physical property.
If through the phase angle of granule of swelling less than 3 degree, then water absorbing capacity can reduce, if greater than 30 degree, then by
Deformation when gel is under pressure is big, and therefore intergranular attachment, the problem that gap is blocked can occur, thus can make through
The permeability reduction of the water-absorbing resins of swelling.For this respect, it is preferably 3 to 20 through the phase angle of the granule of swelling
Degree, more preferably 3 to 10 degree.
It addition, according to described mathematical expression 1, the water-absorbing resins of the present invention meet with the gel phase of artificial urine swelling for
The physical property that phase angle slip is 3 to 35% of the gel of ultra-pure water swelling.Phase angle slip when water-absorbing resins
Meet described in the range of numerical value time, the permeance property of swelling gel accesses the biggest improvement.
If the phase angle slip of the water-absorbing resins according to the present invention is less than 3%, then with the gel of artificial urine swelling
Elastic characteristic insufficient, thus permeability can be reduced, if greater than 35%, then excessively become because of elastic characteristic strong, thus can drop
Low water absorbing capacity.For this respect, phase angle slip is preferably 5 to 35%, and more preferably 10 to 35%.
It addition, according to another concrete example of the present invention, water-absorbing resins disclosure satisfy that particle size distribution is 100 to 1000 μm
Physical property.
When the particle size distribution of described water-absorbing resins is in the range of described, it is possible to prevent from holding because the size of granule is too small
The phenomenon easily dispersed, and, when preparing water-absorbing resins, though apply impact also will not easily fragmentation, and be possible to prevent
Preparation has the problem during water absorption articles for use of uniform thickness.
Hereinafter, the preparation method of the present invention is described in detail.
The water-absorbing resins preparation method of the present invention includes polymerization process, drying process and pulverizing process.Described preparation work
Sequence may further include surface cross-linking process step, and, described preparation section may further include kneading process as required.
Polymerization process according to the present invention can gather by making the polymeric compositions comprising acrylic monomer and cross-linking agent
Close and implement.
Polymeric compositions according to the present invention comprises acrylic monomer, and described acrylic monomer refers to as third
Olefin(e) acid and the monomer of salt thereof.Acrylic acid polymerization can generate acrylates implement by being carried out processing by alkali, such as, and can
To be implemented by process alkali metal hydroxide, ammonia or organic amine etc..Wherein, in order to prepare the suction of more excellent physical property
Water-base resin, is preferably used alkali metal hydroxide to process acrylic acid, such as, uses sodium hydroxide, potassium hydroxide or hydrogen-oxygen
Change lithium to process.In order to improve the water absorbing capacity of water-absorbing resins, in alkali processes, preferably make the neutralization of acrylic acid acidic group
Rate is 60 moles of more than %.
Polymeric compositions according to the present invention comprises cross-linking agent, it is possible to use known crosslinking widely used in the art
Agent, and can be selected from have can be with the compound of the functional group of the water solublity substitution reaction of monomer.For example, it is possible to be selected from
Carbon number be the bisacrylamide of 6 to 12, double Methacrylamide, carbon number be poly-(methyl) of the polyhydric alcohol of 2 to 10
Acrylate and poly-(methyl) allyl ether etc. of polyhydric alcohol that carbon number is 2 to 10, but it is not limited to this.
The usage amount of described cross-linking agent is not particularly limited, it is, for example possible to use be polymerized in the polymer to comprise
Total monomer is the cross-linking agent of 0.001 to 2 mole of %, and 0.005 to 0.5 mole % is preferably used.If the content of cross-linking agent is little
In 0.001 mole of %, then the lowest due to crosslink density, therefore absorb moisture, it would be better to say that and be dissolved in water, if greatly
In 2 moles of %, then the highest due to crosslink density, the expansion that thus be accordingly used in water suction tails off, thus is difficult to obtain sufficiently water suction
Property.
The water-absorbing resins that the present invention provides is owing to being mixed with the elasticity that can improve swelling gel in polymeric compositions
The polysaccharide improving agent as elasticity such that it is able to meet described physical property.Described polysaccharide can make aqueous solution
After remix in polymeric compositions, as long as before the drying step, before polymerization or polymerization after any step in all may be used
To mix.For example, it is possible to mix in polymerization process, it is also possible to kneading process after polymerisation mixes.
Described elastic raising agent is formed as the structure of rigid helical (rigid helix) form for the first time by coagulation
Body, thus demonstrate the elasticity of excellence, if running into the cation comprising potassium and calcium, the most described spiral structure body recondenses,
And form the strong second time coagulation (aggregate) of a kind of crosslink sites etc., thus demonstrate more excellent bullet
Property characteristic.In more detail, when comprising the body fluid that the described elastic water-absorbing resins absorption urine etc. improving agent is discharged from health
Time, the elasticity in water-absorbing resins improves agent and the potassium being contained in body fluid or calcium cation is met, and improves agent so that elastic
Form coagulation.
Under normal circumstances, when evaluating the physical property of water-absorbing resins, use 0.9% sodium chloride only considering ion concentration
Normal saline, but this is variant with actual urine ionic structure.To this, in the present invention, inventor is in order to clearly state bullet
Property improve the effect of agent, employ similar with actual urine, with 0.06% magnesium chloride, 0.04% calcium chloride, 0.3% potassium chloride
And 0.5% artificial urine of regulating of the concentration of sodium chloride.Have identical owing to the urine of people containing with above-mentioned artificial urine
The calcium of composition or potassium ion, therefore meet elasticity raising agent and can form the condition of secondary coagulation.When absorption do not have potassium or calcium from
During the ultra-pure water of son, elastic improve agent and will not form secondary coagulation, thus can only expect to rely on the elastic spiral improving agent
The elastic raising of the formation of structure.Agent, the water-absorbing resins comprising polysaccharide and the tree not comprising it is improved as elasticity
Fat is compared, and during swelling, the elastic excellence under pressure, therefore, will not be easily deformed when water-absorbing resins is under pressure, thus, and swelling
Intergranular gap will not block so that body fluid can pass through between granule well.
As long as described polysaccharide can prepare the material of the water-absorbing resins of the present invention, then less than the object of the invention
In the range of, its kind is not particularly limited, and specifically, such as, can use the polysaccharide used as food thickening agent
Class.Food thickening agent is the material used to give the mouthfeel of such as elasticity etc. to food, and its safety is filled
Divide certification.Therefore, when using food thickening agent in preparing water-absorbing resins, asking in terms of safety will not be produced completely
Topic.As described polysaccharide, such as, can use alginate (Alginate), carrageenan (Carrageenan), pectin, evil spirit
At least one in taro and cellulose, but it is not limited to this.Carrageenan can be used alone K-carrageenan, lambda-carrageenan and I-
Carrageenan, or it is used in mixed way two or more K-carrageenan, lambda-carrageenan and I-carrageenan.
In terms of the acrylic monomer of polymeric compositions, it is possible to use the described polysaccharide of 0.1 to 20 weight %, preferably make
By 0.5 to 10 weight %.More preferably, it is possible to use 1 to 5 weight %.With the total monomer of polymeric compositions, if described many
Saccharide is less than 0.1 weight %, then elastic raising the through the gel of swelling has little effect, if greater than 20 weight %, then because of bullet
Property too strong, not only can not absorb moisture well, and the proportion of composing step-down of absorber that reason acrylic acid is constituted, thus meeting
The water absorbing capacity making water-absorbing resins reduces.
Described polymeric compositions, under atmosphere of inert gases, replaces the oxygen being dissolved in monomer component with noble gas
Time, it is polymerized aspect being used for, can have more suitably physical property.Described noble gas such as can be selected from nitrogen, dioxy
Change carbon or argon etc..
The polymerization of described polymeric compositions can be implemented by the method in thermal polymerization method and light polymerization process,
Or two kinds of method compound uses can be implemented, specifically, as thermal polymerization method, can select to use at 40 to 90 DEG C
At a temperature of be polymerized the general thermal polymerization method of 2 to 30 minutes and be polymerized 2 to 30 points at a temperature of 25 to 50 DEG C relatively low
The redox polymerization process of clock is implemented, and, light polymerization process can be by irradiating ultraviolet at a temperature of 25 to 110 DEG C
Light was implemented for 10 seconds to 20 minutes.When being used in mixed way two kinds of methods, the initial stage polymerization to being compounded with light trigger and thermal initiator
Compositions irradiation ultraviolet radiation implements photopolymerization, and the heat of neutralization produced during by implementing photopolymerization causes thermal initiator to implement
Thermal polymerization, thus be polymerized.Low and there is the aqueous gel shape of more excellent physical property in order to prepare water dissolvable composition
Polymer, is preferably used the light-initiated method with thermal initiation of compound use.
Described polymerization can be implemented by adding polymerization initiator.Can properly select according to polymerization and add
Add known polymerization initiator used in the art.Described polymerization initiator can use selected from azo-initiator, peroxide
Compound class initiator, redox type initiators, organohalogen compounds initiator, 1-Phenylethanone., benzoin, benzophenone, benzyl class
More than one initiator in compound and their derivant.And as Photoepolymerizationinitiater initiater, such as, can use and be selected from
1-Phenylethanone., benzoin, benzophenone, benzyl compounds and as they the diethoxy acetophenone of derivant, 2-hydroxyl-2-
Methyl isophthalic acid-phenyl-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl)-2-propyl group ketone, 4-benzoyl-4 '-methyl-
More than one initiator in diphenyl sulfide and azo compound etc..
The content of described polymerization initiator is not particularly limited, it is, for example possible to use be polymerized in the polymer to comprise
The described polymerization initiator that total monomer is 0.001 to 2 mole of %, 0.01 to 0.1 mole % is preferably used.If polymerization is drawn
Send out agent and be less than 0.001 mole of %, then unreacted residues monomer can increase, and if greater than 2 moles of %, is then difficult to control to polymerization.
The aqueous gel being polymerized described polymeric compositions and obtain, can implement kneading process as required further.
For another concrete example of the present invention, in described kneading process, aqueous gel can improve agent with elasticity and mix.
That is, when polymeric compositions do not comprise elastic improve agent and when being polymerized, elastic improve agent in kneading process can with containing water-setting
Glue mixes.At this moment, kneading process can be by utilizing kneader (kneader), mincer (mincer), planetary-type mixer
The kneader of (planetary mixer) and hammer blender (hammer mixer) etc. is implemented, and, as long as can be by
Aqueous gel and the elastic kneader improving agent mix homogeneously, then to the selection of kneader and use that there is no particular limitation.Pinch
Close the elastic raising agent of interpolation in operation and can use the material identical with the elastic raising agent added in described polymerization process.
Aqueous gel through kneading process can regulate moisture content by drying process.Can be according to prepared aqueous
The moisture content of gel selects the baking temperature in suitable drying process and time conditions, preferably the temperature of 160 to 190 DEG C
Under the conditions of carry out 20 minutes to 40 minutes.If baking temperature is less than 160 DEG C, then drying effect is low, thus when can extend dry
Between, if baking temperature is higher than 190 DEG C, then easily pulverizes because aqueous gel surface is excessively dried, thus powder content can increase
Add.If powder content increases, then can extend the time of micropowder removing step, thus reduce productivity.By described back tender
Sequence and the moisture content of aqueous gel that obtains can be 1 to 10 weight %.
Aforesaid water-absorbing resins is generally ground into powder and uses.Through dry aqueous gel at pulverizing process
In crushed, as long as and resin pulverize in normally used breaking method, then can select to make with being not limited by the structure
With.For example, it is possible to utilize needle mill (pin mill), hammer mill (hammer mill), screw rod grinding machine (screw mill) and cold
The reducing mechanism of agar crushing device (freezer mill) etc. is pulverized.Generally, the water-absorbing resins used in product
Granular size is preferably 100 to 1000 μm.
The described water-absorbing resins through pulverizing, after pulverizing, can be processed by further enforcement cross-linking agent
Operation regulates surface crosslinking density, and can improve the granule strength of water-absorbing resins by described cross-linking process step and add
Pressure water absorbent rate.
Preferably, described cross-linking agent is selected from dihydroxylic alcohols (diol) or glycol (glycol) the class chemical combination that carbon number is 2 to 8
Thing.
Described dibastic alcohol compound, specifically can enumerate such as 1,3-PD, 2,3,4-trimethyl-1,3-penta 2
Alcohol, 2-butylene-1,4-glycol, 1,4-butanediol, 1,3 butylene glycol, 1,5-pentanediol, 1,6-HD and 1,2-hexamethylene diformazan
Alcohol, polycarbonate polyol etc., these can individually use, or mix two or more use.
Described glycol compound, specifically can enumerate such as monoethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), poly-second two
Alcohol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerol and polyglycereol etc., these can individually use, or mixing two kinds
More than use.
Hereinafter, proposing preferred embodiment to strengthen the understanding of the present invention, these embodiments are merely to illustrate
The present invention, the right not limiting the present invention is wanted protection domain, and be it will be appreciated by those skilled in the art that the model in the present invention
In farmland and technical scope, it is possible to implement the various deformation to embodiment and change further, and these deformation and change all include
In the claims of the present invention.
Embodiment 1
Make the acrylic acid of 400g and ultra-pure water (the Mili-Q integral 3 of 340g；Millipore Corp.) mixing, and prepare
Acrylic acid mixed solution.After being dissolved in the ultra-pure water of 400g with the sodium hydroxide (NaOH) that acrylic acid is 70 moles of %,
It is cooled to 10 DEG C, the most slowly puts in acrylic acid mixed solution.Under the conditions of 10 DEG C, implement nitrogen purging (pur ging)
30 minutes, afterwards, add the potassium metabisulfite (K of 0.4915g2S2O8), the 1-hydroxycyclohexyl phenyl ketone of 0.2457g.Add
Sodium bicarbonate (the NaHCO of 2.457g3After), irradiate 1mw/cm immediately2Ultraviolet light 1 minute, and after removing light, place 6 minutes,
Thus obtain aqueous gel.The aqueous gel obtained is cut into 1cm3Size after, weighing is 0.1 weight with described acrylic acid
Part K-carrageenan, and be prepared as 10% aqueous solution, then make its together with aqueous gel by bell-type blender (SFD-G:
SHINSUNG company).Make by bell-type blender mixture out again by bell-type blender, thus mediate completely.Profit
With forced circulation drying machine (OF-02PW；Jie Aote (JEIO TECH) company) it is dried.Initial stage is from 30 DEG C to 100 DEG C of intensifications
Behind 5 minutes, and dry 10 minutes, again it is warming up to 120 DEG C and is dried 10 minutes, be warming up to 150 DEG C the most again and be dried 10 minutes,
It is warming up to 180 DEG C eventually be dried 25 minutes.After drying, preserve in by dry air (Dried Air) substituted chamber (chamber)
Sample, until sample is cooled to room temperature.Pulverize through overcooled solid content described, and utilize screen cloth only to filter out 150
Granule to 850 μm.Described pulverizing is to utilize freezing crusher (Freezer/Mill 6870；SPEX Sample Prep is public
Department) implement under the atmosphere of liquid nitrogen, implement 30 minutes altogether.Utilize PCP-500 (propylene carbonate ester polyol (Propylene
carbonate polyol)；SK company), the granule filtered out is carried out surface-crosslinked.The surface crosslinking agent of 4.23g is dissolved
After in the ethanol of 7g, it is slowly added to the water of 7g, and after preparing surface-crosslinked liquid compositions, is set as " weak " at stirring intensity
Homogenizer (HMF-3260S；Hani that Co., Ltd. In), by above-mentioned surface-crosslinked liquid compositions with described
After granule uniformly mixes, react 20 minutes at 180 DEG C, thus finally prepare water-absorbing resins.Use silicon by described high-speed stirring
The blade mixing machine is processed into toroidal so that water-absorbent besin particles will not be pulverized because of blade.
Embodiment 2 to 7
In addition to use elastic raising agent with the content shown in table 1 below, by method same as in Example 1
Prepare water-absorbing resins.
Embodiment 8
Make the acrylic acid of 400g and ultra-pure water (the Mili-Q integral 3 of 340g；Millipore Corp.) mixing, and prepare
Acrylic acid mixed solution.By the sodium hydroxide (NaOH) of 70 moles of % with acrylic acid be 0.1 weight portion with acrylic acid
Carrageenan (aldrich company) be dissolved in the ultra-pure water of 400g after, be cooled to 10 DEG C, the most slowly put into acrylic acid
In mixed solution.Under the conditions of 10 DEG C, implement nitrogen purge 30 minutes, afterwards, add the potassium metabisulfite of 0.4915g
(K2S2O8), the 1-hydroxycyclohexyl phenyl ketone of 0.2457g.Add the sodium bicarbonate (NaHCO of 2.457g3After), irradiate immediately
1mw/cm2Ultraviolet light 1 minute, and after removing light, place 6 minutes, thus obtain aqueous gel.The aqueous gel obtained is cut
Become 1cm3Size after, utilize forced circulation drying machine (OF-02PW；Jie Aote company) it is dried.Initial stage is from 30 DEG C to 100
DEG C heat up 5 minutes, and be dried after 10 minutes, be again warming up to 120 DEG C and be dried 10 minutes, be warming up to 150 DEG C the most again and be dried 10
Minute, finally it is warming up to 180 DEG C and is dried 25 minutes.After drying, in the chamber replaced by dry air, preserve sample, until sample
It is cooled to room temperature.Pulverize through overcooled solid content described, and utilize screen cloth only filter out 150 to 850 μm
Grain.Described pulverizing is by utilizing freezing crusher (Freezer/Mill 6870；SPEX SamplePrep company) at liquid
Implement under the atmosphere of nitrogen, implement 30 minutes altogether.Utilize PCP-500 (propylene carbonate ester polyol；SK company), to filter out
Granule carries out surface-crosslinked.After the surface crosslinking agent of 4.23g is dissolved in the ethanol of 7g, it is slowly added to the water of 7g, and prepares
After surface-crosslinked liquid compositions, it is set as homogenizer (the HMF-3260S of " weak " at stirring intensity；Hani that Co., Ltd.)
In, after above-mentioned surface-crosslinked liquid compositions is uniformly mixed with described granule, react 20 minutes at 180 DEG C, thus standby final
Prepare water-absorbing resins.Use silicon that the blade of described homogenizer is processed into toroidal so that water-absorbent besin particles is not
Can pulverize because of blade.
Embodiment 9 to 11
In addition to using the elastic content improving agent as shown in table 1 below, by method the same as in Example 8
Prepare water-absorbing resins.
Embodiment 12 to 13
Use except alginate is improved agent as elasticity, and as shown in table 1 below, use elastic raising agent
Beyond content, prepare water-absorbing resins by method same as in Example 1.
Embodiment 14 to 15
Use except alginate is improved agent as elasticity, and use elasticity with the content shown in table 1 below
Improve beyond agent, prepare water-absorbing resins by method the same as in Example 8.
Comparative example 1
In addition to not adding elastic raising agent, implement according to the same manner as in Example 1.
Comparative example 2 and 4
In addition to using the elastic kind improving agent and usage amount as shown in table 1 below, by with embodiment 1 phase
Same method prepares water-absorbing resins.
Comparative example 3 and 5
In addition to using the elastic kind improving agent and usage amount as shown in table 1 below, by with embodiment 8 phase
Same method prepares water-absorbing resins.
Table 1
Test example
Using sample identical for water dissolvable composition as object, measured by described embodiment by following method and compare
The physical property of the water-absorbing resins prepared in example, and the results are shown in table 2 below.
1. add pressure water absorbent rate (AUL) to measure
Adding the absorptive mensuration of pressure is that the device utilizing Fig. 1 measures.Determinator is by A1: hammer (0.3psi), A2:
Cylinder, A4: non-woven fabrics, A5: paper filter, A6: glass filter, A7: glass filter support platform, A9: cylinder support platform,
A10: container, A11: connecting tube, A12: aqua storage tank is constituted, and is arranging and is adding the pressure following institute of assay method to water absorbent rate
State.
Connect cylinder by connecting tube A11 and support platform A9 and aqua storage tank A12, each device is equipped with hole, so that in aqua storage tank
0.9% saline A13 can move.Cylinder supports platform A9 be placed in container A 10, and utilize glass filter to support platform A7
The top making glass filter A6 supports the highly consistent of platform A9 top with cylinder.Afterwards, placement supports the upper of platform A9 than cylinder
The paper filter A5 that portion is bigger.Open the stopper of aqua storage tank A12, make saline A13 flow out, so that the saline moved by pipeline
A13 fills cylinder and supports the top of platform A9, and makes the saline of excess be naturally discharged into the appearance of outside by paper filter A5
In device.If having bubble between glass filter A6 and paper filter A5, then remove.
In the cylinder A2 that bottom is wrapped up by non-woven fabrics A4, the water-absorbing resins of 0.9g (w0) is laid on non-woven fabrics
A3, places cylinder, and the face that is placed on it by hammer A1 immediately afterwards on paper filter.
After 1 hour, reclaim the aqueous gel in cylinder, and gravimetry (w1, the weight of the water-absorbing resins after water suction),
And deduct the weight (w0, the weight of the water-absorbing resins before water suction) measuring sample, by the value obtained divided by measuring sample
Weight (w0), thus obtain and add pressure water absorbent rate.
[mathematical expression 2]
Add pressure water absorbent rate (g/g)=(water-absorbing resins before the weight (w1) of the aqueous gel after water suction-water suction
Weight (w0)) weight (w0) of water-absorbing resins before/water suction.
The preparation method of the normal saline used in the described mensuration adding pressure water absorbent rate is as follows.Weigh the chlorination of 6g
Sodium, the potassium chloride of 4g, the calcium chloride of 0.6g, 0.3g magnesium chloride after, add ultra-pure water and be adjusted to 1000g, and stir 1 hour
And prepare.
2. phase angle measures
Utilize advanced Rheometric Expansion System flow graph (Advanced Rheometric Expansion System；TA is public
Department) parallel-plate, with dynamic frequency scanning (Dynamic frequency sweep) pattern, obtain the water-absorbing resins of acquisition
Tan δ (shear rate=100rad/s) value after, be converted into phase angle (δ), i.e. arctan value.Described mensuration is by flat
Pile up on andante more than 5mm after the gel of swelling, by gap (gap) the furnishing 1.8mm of advanced Rheometric Expansion System, and
Make not to be sufficient filling with there is no gap.Measuring temperature and be set as 35 DEG C, tension force (strain) is set as 5%.
While swelling gel is the described artificial urine rotating 20g with 500rpm, by fast for the water-absorbing resins of the acquisition of 1g
Speed is put between whirlpool central part and flask walls, and treats water-absorbing resins to fully absorb artificial urine and make water-absorbing resins swelling
20 times.
3. the mensuration of phase angle slip (%)
Under the condition determination identical with phase angle mensuration, obtain respectively with the gel of ultra-pure water swelling and with described manually
Behind the phase angle of the gel of urine swelling, substitute in described mathematical expression 1, thus calculate phase angle slip.
4. permeability determination
The water-absorbing resins of acquisition is measured according to the assay method described in US granted patent the 8,466,228th
Permeability.
Table 2
See table 2 it has been confirmed that in polymerization process or kneading process, be calculated as 0.1 to 20 weight with acrylic monomer
The elastic suction improving agent and making its embodiments of the invention 1 to 15 being included in water-absorbing resins is added in the range of amount %
Water-base resin, compared with not adding the elastic comparative example 1 improving agent, maintains the high of 20 to 45g/g to add pressure water absorbent rate
While, demonstrate 3*10-8cm2Above high permeability.If permeability is less than 3*10-8cm2, then liquid is not easy infiltration,
And simply absorb moisture locally, thus cause the volume increase of specific part or liquid to flow on top layer.
The phase angle of the gel carrying out swelling with artificial urine and ultra-pure water respectively in embodiments of the invention 1 to 15 is reduced
Rate is increased compared to not adding the elastic comparative example 1 improving agent.This represents that elasticity improves the ion of agent and artificial urine
Produce reaction, improve so that elastic.
Therefore, the water absorbing capacity of the product of Application Example is excellent, and also maintains water absorption when swelling
The elasticity of resin, thus reduce intergranular attachment, it is therefore contemplated that it is able to maintain that the water absorption of excellence.
It has been confirmed that the phase angle of swelling gel can be along with the elastic raising added from embodiments of the invention 1 to 7
The increase of the content of agent and reduce.This represents the elastic increase of swelling gel, and can confirm elasticity by permeability value
Increase make permeability be increased.In contrast, it appeared that add pressure water absorbent rate and can improve along with the elasticity added
The increase of the content of agent and reduce therewith after increasing to certain content.This can be understood as due to water absorbing capacity excellence
The ratio of components of acrylic acid absorber reduces, and therefore water suction physical property itself declines.
Although the resin using the elastic comparative example 2 to 5 improving agent more than 20 weight % shows the least phase
Parallactic angle and the permeability of excellence, but can confirm that owing to excess with the addition of elastic raising agent, the therefore group of acrylic acid absorber
Become ratio to reduce, thus cause water absorbing capacity to reduce.
Claims (13)
1. the preparation method of a water-absorbing resins, it is characterised in that the preparation method of described water-absorbing resins includes following step
Rapid: to make the polymeric compositions polymerization comprising acrylic monomer, polysaccharide and cross-linking agent；And be dried and pulverize through above-mentioned poly-
The aqueous gel closed and obtain, and, in terms of the acrylic monomer of polymeric compositions, comprise described in 0.1 to 20 weight %
Polysaccharide.
The preparation method of water-absorbing resins the most according to claim 1, it is characterised in that described polysaccharide is selected from alginic acid
At least one in salt, K-carrageenan, I-carrageenan, lambda-carrageenan, pectin, Rhizoma amorphophalli and cellulose.
The preparation method of water-absorbing resins the most according to claim 1, it is characterised in that with the acrylic acid of polymeric compositions
Class monomer meter, comprises the described polysaccharide of 0.5 to 10 weight %.
4. the preparation method of a water-absorbing resins, it is characterised in that the preparation method of described water-absorbing resins includes following step
Rapid: to make the polymeric compositions polymerization comprising acrylic monomer and cross-linking agent；Mix and mediate and obtain through above-mentioned polymerization
Aqueous gel and polysaccharide；And it is dried and pulverizes the described aqueous gel through mediating, and, with the propylene of polymeric compositions
Acrylic monomer meter, comprises the described polysaccharide of 0.1 to 20 weight %.
The preparation method of water-absorbing resins the most according to claim 4, it is characterised in that described polysaccharide is selected from alginic acid
At least one in salt, K-carrageenan, I-carrageenan, lambda-carrageenan, pectin, Rhizoma amorphophalli and cellulose.
The preparation method of water-absorbing resins the most according to claim 5, it is characterised in that with the acrylic acid of polymeric compositions
Class monomer meter, comprises the described polysaccharide of 0.5 to 10 weight %.
7. a water-absorbing resins, it is characterised in that pressure water absorbent rate (AUL) that adds of described water-absorbing resins is 20 to 45g/
g；The phase angle (δ) of swelling gel is 3 to 30 degree；Phase angle slip (%) is 3 to 35%.
Water-absorbing resins the most according to claim 7, it is characterised in that described water-absorbing resins add pressure water absorbent rate
(AUL) it is 30 to 45g/g.
Water-absorbing resins the most according to claim 7, it is characterised in that the phase place of the swelling gel of described water-absorbing resins
Angle (δ) is 3 to 20 degree.
Water-absorbing resins the most according to claim 7, it is characterised in that the phase of the swelling gel of described water-absorbing resins
Parallactic angle (δ) is 3 to 10 degree.
11. water-absorbing resins according to claim 7, it is characterised in that the phase angle slip of described water-absorbing resins
(%) be 5 to 35%.
12. water-absorbing resins according to claim 7, it is characterised in that the phase angle slip of described water-absorbing resins
(%) be 10 to 35%.
13. water-absorbing resins according to claim 7, it is characterised in that the particle size distribution of described water-absorbing resins is 100
To 1000 μm.
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| KR1020150015494A KR101596624B1 (en) | 2015-01-30 | 2015-01-30 | Absorbent polymer and method of preparing the same |
| KR10-2015-0015494 | 2015-01-30 |
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| CN105838009A true CN105838009A (en) | 2016-08-10 |
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| US (1) | US20160220724A1 (en) |
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| CN106590271B (en) * | 2016-12-07 | 2019-02-19 | 温州任和文化创意有限责任公司 | Material water-proof material is used in a kind of cable brushing filling |
| JP6843261B2 (en) | 2017-08-25 | 2021-03-17 | エルジー・ケム・リミテッド | SAP evaluation device |
| KR102293184B1 (en) * | 2019-09-16 | 2021-08-25 | 한국원자력연구원 | Composition for absorbent composite, absorbent composite prepared using the same and method for preparing the same |
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| CN1172124A (en) * | 1996-07-25 | 1998-02-04 | 化学工业部北京化工研究院 | Wate-absorption resin and preparing method thereof |
| CN1325313A (en) * | 1998-11-09 | 2001-12-05 | 花王株式会社 | Products for thickening processing bodily fluids or bodily wastes |
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| CN1772779A (en) * | 2005-10-28 | 2006-05-17 | 中国林业科学研究院林产化学工业研究所 | Super electrolyte resistant high water absorption resin and its prepn |
| CN103724552A (en) * | 2012-10-12 | 2014-04-16 | 马群 | Novel preparation process of super water absorbent |
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| US7169843B2 (en) | 2003-04-25 | 2007-01-30 | Stockhausen, Inc. | Superabsorbent polymer with high permeability |
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| WO2012128264A1 (en) * | 2011-03-24 | 2012-09-27 | 三洋化成工業株式会社 | Aqueous-liquid-absorbable resin, aqueous-liquid-absorbable composition, and absorber material and absorbable object each produced using same |
| JP6013729B2 (en) * | 2011-12-27 | 2016-10-25 | 株式会社リブドゥコーポレーション | Water-absorbent resin powder and absorbent body and absorbent article using the same |
-
2015
- 2015-01-30 KR KR1020150015494A patent/KR101596624B1/en active IP Right Grant
-
2016
- 2016-01-25 CN CN201610048746.9A patent/CN105838009A/en active Pending
- 2016-02-01 US US15/011,731 patent/US20160220724A1/en not_active Abandoned
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| US5145906A (en) * | 1989-09-28 | 1992-09-08 | Hoechst Celanese Corporation | Super-absorbent polymer having improved absorbency properties |
| CN1172124A (en) * | 1996-07-25 | 1998-02-04 | 化学工业部北京化工研究院 | Wate-absorption resin and preparing method thereof |
| CN1325313A (en) * | 1998-11-09 | 2001-12-05 | 花王株式会社 | Products for thickening processing bodily fluids or bodily wastes |
| CN1715304A (en) * | 2004-06-29 | 2006-01-04 | 北京理工大学 | Process for preparing cellulose modified high water absorption resin |
| CN1733815A (en) * | 2005-04-28 | 2006-02-15 | 华南师范大学 | Preparation method of high-intensity water absorbent material |
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| KR101596624B1 (en) | 2016-02-22 |
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